JP4374460B2 - Method for solvent extraction of Nd (III) from aqueous nitric acid solution and extractant therefor - Google Patents
Method for solvent extraction of Nd (III) from aqueous nitric acid solution and extractant therefor Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 title claims description 15
- 238000000638 solvent extraction Methods 0.000 title claims description 14
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 238000000605 extraction Methods 0.000 claims description 14
- 239000002915 spent fuel radioactive waste Substances 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000010808 liquid waste Substances 0.000 claims description 4
- 230000002285 radioactive effect Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000002927 high level radioactive waste Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 claims 2
- CNDWHJQEGZZDTQ-UHFFFAOYSA-N 2-(2-amino-2-oxoethoxy)acetamide Chemical compound NC(=O)COCC(N)=O CNDWHJQEGZZDTQ-UHFFFAOYSA-N 0.000 description 20
- -1 diglycolamide compound Chemical class 0.000 description 18
- 239000012071 phase Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 229910052768 actinide Inorganic materials 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- 229940094933 n-dodecane Drugs 0.000 description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- VRZYWIAVUGQHKB-UHFFFAOYSA-N 2-[2-(dioctylamino)-2-oxoethoxy]-n,n-dioctylacetamide Chemical compound CCCCCCCCN(CCCCCCCC)C(=O)COCC(=O)N(CCCCCCCC)CCCCCCCC VRZYWIAVUGQHKB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JCKYMEVQNKNLIB-UHFFFAOYSA-N O[N+]([O-])=O.CCCCCCCCCCCC Chemical compound O[N+]([O-])=O.CCCCCCCCCCCC JCKYMEVQNKNLIB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910021644 lanthanide ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 238000003608 radiolysis reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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Description
本発明は、硝酸−ドデカン両相を用いて溶媒抽出をする際に、長鎖アルキル基を結合させたジグリコールアミド化合物（ＤＧＡ）により第三相の生成を抑制する方法、および効率的に３、４価のアクチノイドイオンを抽出する方法に関わる。 The present invention relates to a method for suppressing the formation of a third phase by a diglycolamide compound (DGA) to which a long-chain alkyl group is bonded when solvent extraction is performed using both phases of nitric acid and dodecane. The present invention relates to a method for extracting tetravalent actinoid ions.
硝酸水溶液から高濃度の金属元素を工業規模で分離する要請は、使用済み核燃料（ＳＦ）の再処理及び高レベル放射性廃液（ＨＬＬＷ）の処理において生じている。これらの溶解液は硝酸酸性溶液であり、高濃度のアクチノイド元素や核分裂生成元素を含んでいる。これらの元素を分離回収するためには、大量の試料取り扱いが可能であり、反応性が極めて早いという理由から、溶媒抽出法が広範に採用されている。しかしながら、酸性度、金属濃度が高い条件では溶媒抽出の過程で第三相が生成されてしまい、これがプロセス開発にとって大きな障害となっている。 The demand for separation of high concentrations of metallic elements from aqueous nitric acid solutions on an industrial scale has arisen in the reprocessing of spent nuclear fuel (SF) and in the treatment of high level radioactive liquid waste (HLLW). These solutions are acidic nitric acid solutions and contain high concentrations of actinide elements and fission products. In order to separate and recover these elements, a large amount of sample can be handled and the solvent extraction method has been widely adopted because of its extremely fast reactivity. However, under conditions where acidity and metal concentration are high, a third phase is generated in the process of solvent extraction, which is a major obstacle for process development.
第三相の生成を抑制するためには、抽出剤を溶解する希釈剤にモノアミドやリン酸トリブチル（ＴＢＰ）を改質剤として添加する方法や、ニトロベンゼン、オクタノールなど極性の高い溶媒を用いる方法が検討されている。 In order to suppress the formation of the third phase, there are a method of adding monoamide or tributyl phosphate (TBP) as a modifier to a diluent that dissolves the extractant, and a method of using a highly polar solvent such as nitrobenzene or octanol. It is being considered.
上記のような混合溶媒や極性溶媒を用いる方法については、以下に述べる問題点がある。
すなわち、混合溶媒系では、複数の有機物が存在するようになることである。使用が検討されているモノアミド、ＴＢＰはいずれも金属イオンとの反応性が高いため、分配比の精密な評価が難しくなる。また、放射線分解した場合には、副生成物が多く存在するようになるため、それらの検討の必要性からプロセス設計はより複雑になり、モノアミド、ＴＢＰともに更に高い濃度（目的の抽出剤の５〜１０倍）が要求され、分離抽出コストは増大する。加えて、有機相への硝酸の抽出量も増えるため、速やかに逆抽出できなくなる。特に、ＴＢＰはその構造にリンを含むため、これが２次廃棄物発生の要因となりうる。
The method using a mixed solvent or a polar solvent as described above has the following problems.
That is, in the mixed solvent system, a plurality of organic substances are present. Since monoamide and TBP that are being studied for use are both highly reactive with metal ions, it is difficult to accurately evaluate the distribution ratio. In addition, in the case of radiolysis, since many by-products are present, the process design becomes more complicated due to the necessity of studying them, and both monoamide and TBP have higher concentrations (5 of the target extractant). 10 times), and the cost of separation and extraction increases. In addition, since the amount of nitric acid extracted into the organic phase increases, it becomes impossible to back-extract quickly. In particular, since TBP contains phosphorus in its structure, this can be a factor in generating secondary waste.
一方、極性溶媒の使用について、上に示したニトロベンゼン、オクタノールなどの有機溶媒は毒性・危険性がドデカンに比べて高く、取り扱いに注意を要する。また、極性溶媒は水との親和性が高く、水相への分配を検討しなければならず、その場合に分配比が変動する恐れがある。ｎ−ドデカンが放射線分解しても炭化水素が発生するだけであるが、オクタノールが分解すると、その生成物にはＯＨが存在し、これは水溶性で反応性の高いことから、第三相の生成に繋がってしまう。
したがって、本発明は、使用済み燃料溶解液又は高レベル放射性廃液のような硝酸水溶液から硝酸−ドデカン両相を用いて金属イオンを溶媒抽出する際に、第三相の生成を抑制することを課題とするものである。 Therefore, the present invention has an object to suppress the generation of the third phase when solvent extraction of metal ions using nitric acid-dodecane both phases from an aqueous nitric acid solution such as spent fuel solution or high-level radioactive waste liquid. It is what.
上記課題を解決するため本発明者らは鋭意研究した結果、長いアルキル差を有するジグリコールアミド（ＤＧＡ）をドデカンに添加した抽出剤を用いることにより第三相の生成が抑制されることを発見し、本発明を完成させた。 As a result of diligent research, the present inventors have found that the formation of the third phase is suppressed by using an extractant in which diglycolamide (DGA) having a long alkyl difference is added to dodecane. The present invention has been completed.
要するに、本発明は、使用済み燃料（ＳＦ）溶解液又は高レベル放射性廃液（ＨＬＬＷ）のような硝酸水溶液から金属イオンを溶媒抽出する方法において、高い親油性を示すＮ，Ｎ，Ｎ’，Ｎ’−テトラドデシル１，３−オキサペンタンジアミド（ＴＤｄＤＧＡ）をドデカンに希釈した溶媒を用いることにより、第三相の生成を抑制することを特徴とするものである。
In short, the present invention relates to N, N, N ′, N that exhibits high lipophilicity in a method of solvent extraction of metal ions from an aqueous nitric acid solution such as spent fuel (SF) solution or high-level radioactive liquid waste (HLLW). By using a solvent obtained by diluting ' -tetradodecyl 1,3-oxapentanediamide (TDdDGA) in dodecane, the formation of the third phase is suppressed.
また、本発明は、硝酸水溶液から３価若しくは４価のアクチノイドイオン又はランタノイドイオンを溶媒抽出分離するための、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラドデシル１，３−オキサペンタンジアミド（ＴＤｄＤＧＡ）を含むドデカン抽出剤を課題解決手段とする。
The present invention also relates to N, N, N ′, N′- tetradodecyl 1,3-oxapentanediamide (TDdDGA) for solvent extraction and separation of trivalent or tetravalent actinoid ions or lanthanoid ions from an aqueous nitric acid solution. Dodecane extractant containing
本発明にしたがって、長いアルキル鎖を有するジグリコールアミドをドデカンに溶解した抽出剤を用いて溶媒抽出することにより、第三相が生成されることなく、硝酸酸性溶液中に高濃度で含まれる３価若しくは４価のランタノイドイオン、アクチノイドイオンを溶媒抽出分離することができる。 According to the present invention, a third phase is not generated by solvent extraction using an extractant in which diglycolamide having a long alkyl chain is dissolved in dodecane. Divalent or tetravalent lanthanoid ions and actinoid ions can be separated by solvent extraction.
本発明者らは、酸性度が高く、金属濃度が高い溶液から３価若しくは４価のランタノイドイオン又はアクチノイドイオンを効率よく抽出することができ、固体廃棄物の発生源となる金属やリンを含まない組成を有し、無極性溶媒にもよく溶けるジグリコールアミド（ＤＧＡ）化合物を開発した。すなわち、三座配位子のＤＧＡ化合物のひとつである、ＴＤｄＤＧＡ（Ｎ，Ｎ，Ｎ’，Ｎ’−テトラドデシル−１，３−オキサペンタンジアミド）を開発した。
The inventors of the present invention can efficiently extract trivalent or tetravalent lanthanoid ions or actinoid ions from a solution having high acidity and high metal concentration, and include metals and phosphorus that are sources of solid waste. Diglycolamide (DGA) compounds have been developed that have a low composition and are well soluble in nonpolar solvents. That is, TD d DGA (N, N, N ′, N′-tetradodecyl-1,3-oxapentanediamide), which is one of tridentate DGA compounds, was developed.
したがって本発明は、使用済み燃料溶解液又は高レベル放射性廃液のような硝酸水溶液から金属イオンを溶媒抽出する方法であって、高い親油性を示すＴＤｄＤＧＡをドデカンに希釈した溶媒を用いることにより、第三相の生成を抑制することを特徴とするものである。
Therefore, the present invention is a method for solvent extraction of metal ions from an aqueous nitric acid solution such as spent fuel solution or high-level radioactive liquid waste, and uses a solvent obtained by diluting TDdDGA showing high lipophilicity in dodecane. It is characterized by suppressing the formation of three phases.
本発明において、ＤＧＡの濃度は、抽出すべき金属イオンの濃度に依存して決定することができる。
本発明においてドデカン抽出剤に添加するＤＧＡ化合物は、長い炭化水素鎖を有し、極性が著しく低いため、無極性溶媒であるｎ−ドデカンと非常によく混ざり合う。また、ＤＧＡ化合物の金属錯体はドデカン中で非常に安定であり、過剰金属濃度に由来する第三相が殆ど生成されないという特徴を有する。ｎ−ドデカンにＴＤｄＤＧＡを添加した本発明の抽出剤は、３価若しくは４価のランタノイドイオン又はアクチノイドイオンに対して高い抽出能力を示す。
In the present invention, the concentration of DGA can be determined depending on the concentration of metal ions to be extracted.
In the present invention, the DGA compound added to the dodecane extractant has a long hydrocarbon chain and is extremely low in polarity, so it mixes very well with n-dodecane, which is a nonpolar solvent. In addition, the metal complex of the DGA compound is very stable in dodecane and has a feature that the third phase derived from the excess metal concentration is hardly generated. extractant of the present invention with the addition of TD d DGA in n- dodecane, exhibit high extraction capability with respect to trivalent or tetravalent lanthanide ions or actinide ions.
前述の従来の抽出剤使用に起因する欠点に関連して、本発明の抽出剤の利点をまとめると以下の通りである。
（１）その組成に炭素、水素、酸素、窒素しか含まず、完全焼却処理が可能であるため、固体廃棄物は殆ど発生しない。
The advantages of the extractant of the present invention are summarized as follows in relation to the above-mentioned drawbacks caused by the use of the extractant.
(1) Since the composition contains only carbon, hydrogen, oxygen, and nitrogen and can be completely incinerated, almost no solid waste is generated.
（２）本発明の抽出剤は既存プロセスで使用実績のあるドデカンのような無極性溶媒に非常によく溶ける。このことはいかなる溶媒でも対応可能であることを示す。
（３）本発明の抽出剤は、疎水性が非常に高く有機相中の金属イオンの増加による第三相の生成を抑制することができ、更により多くの金属イオンを有機相中に抽出可能である。
(2) The extractant of the present invention is very soluble in nonpolar solvents such as dodecane that have been used in existing processes. This indicates that any solvent can be used.
(3) The extractant of the present invention is very hydrophobic and can suppress the formation of the third phase due to the increase of metal ions in the organic phase, and more metal ions can be extracted into the organic phase. It is.
（４）本発明の抽出剤は、２種類の有機化合物を希釈剤に添加する従来の混合溶媒系抽出剤より、プロセス評価が容易であり、分解生成物の特定も容易でその影響が少ない。また、硝酸の抽出が少ないため、逆抽出を効率的に行うことができる。 (4) The extractant of the present invention is easier to evaluate than the conventional mixed solvent extractant in which two kinds of organic compounds are added to the diluent, and the decomposition product is easily identified and less affected. Moreover, since there is little extraction of nitric acid, back extraction can be performed efficiently.
（５）より毒性、危険性の高い希釈剤を使う必要がない。
（６）本発明の抽出剤は、水への溶解度が極めて低く、抽出剤の水相への分配を評価する必要がない。また、プロセスでの経済性評価などに重要な、相分離の迅速性も期待される。
(5) It is not necessary to use a more toxic and dangerous diluent.
(6) The extractant of the present invention has extremely low solubility in water, and it is not necessary to evaluate the distribution of the extractant into the aqueous phase. In addition, rapid phase separation, which is important for evaluating economics in processes, is also expected.
（参考例１）
トレーサー量のＡｍ（III）を含む０．９４Ｍ硝酸溶液から、種々の濃度の３種のＤＧＡ化合物（ＴＯＤＧＡ：Ｎ，Ｎ’，Ｎ，Ｎ’−テトラオクチル−１，３−オキサペンタンジアミド、ＴＤＤＧＡ：Ｎ，Ｎ’，Ｎ，Ｎ’−テトラデシル−１，３−オキサペンタンジアミド、ＴＤｄＤＧＡ：Ｎ，Ｎ’Ｎ，Ｎ’−テトラドデシル−１，３−オキサペンタンジアミド）をｎ−ドデカン溶媒に溶解した抽出剤を用いて上記金属を抽出した。平衡時のＡｍ（III）の抽出分配比（Ｄ、２５℃）のＤＧＡ化合物濃度依存性について図１に示す。
( Reference Example 1)
From 0.94M nitric acid solution containing tracer amounts of Am (III), 3 kinds of DGA compound at various concentrations (TODGA: N, N ', N, N'- tetra octyl - 1, 3-oxa-pentane diamide, TDDGA: N, N ', N , N'- tetradecyl - 1, 3-oxa-pentane diamide, TD d DGA: N, N'N , N'- tetra-dodecyl - 1, 3-oxa-pentane diamide) the n- dodecane The metal was extracted using an extractant dissolved in a solvent. FIG. 1 shows the DGA compound concentration dependence of the extraction distribution ratio (D, 25 ° C.) of Am (III) at equilibrium.
平衡時のＡｍ（III）の抽出分配比は、水相の硝酸濃度０．９４Ｍ、ＤＧＡ化合物０．１Ｍの場合に１５〜２６の範囲であった。この結果から、金属とＤＧＡとの抽出反応において、Ａｍ（III）：ＴＯＤＧＡのモル比が１：３の金属錯体ができると考えられる。 The extraction distribution ratio of Am (III) at the time of equilibration was in the range of 15 to 26 when the nitric acid concentration in the aqueous phase was 0.94 M and the DGA compound was 0.1 M. From this result, it is considered that a metal complex having an Am (III): TODGA molar ratio of 1: 3 can be formed in the extraction reaction between the metal and DGA.
（実施例２）
５〜４５ｍＭ Ｎｄ（III）を含む３Ｍ ＨＮＯ3から、０．１Ｍ ＤＧＡ／ｎ−ドデカン溶媒によって上記金属を抽出した。有機相中に抽出されたＮｄ（III）濃度と初期（抽出前）水相中のＮｄ（III）濃度との関係（２５℃）を図２に示す。
(Example 2)
The metal was extracted from 3M HNO 3 containing 5-45 mM Nd (III) with 0.1M DGA / n-dodecane solvent. FIG. 2 shows the relationship (25 ° C.) between the Nd (III) concentration extracted in the organic phase and the Nd (III) concentration in the initial (before extraction) aqueous phase.
図２において、初期水相中のＮｄ（III）濃度が増加すると有機相中に抽出されるＮｄ（III）濃度も増加するが、ＴＯＤＧＡ、ＴＤＤＧＡを溶解した抽出剤では極大値を示した後、水相濃度増大とともに減少する傾向があった。これは第三相の生成のためと考えられる。一方、ＴＤｄＤＧＡを溶解した系では、実験した範囲において極大を示すことなく、有機相中Ｎｄ（III）濃度は徐々に増加することが観察された。このことはＴＤｄＤＧＡを溶解した抽出剤系では第三相を生成することなく、初期水相中のＮｄ（III）濃度の増加に伴い有機相への抽出量は理想的な抽出容量値に近づいていくことを示すものである。
In FIG. 2, as the Nd (III) concentration in the initial aqueous phase increases, the Nd (III) concentration extracted in the organic phase also increases. However, the extractant dissolved with TODGA and TDDGA shows a maximum value, There was a tendency to decrease with increasing aqueous phase concentration. This is thought to be due to the formation of the third phase. On the other hand, in the system in which TD d DGA was dissolved, it was observed that the Nd (III) concentration in the organic phase gradually increased without exhibiting a maximum in the experimental range. This means that in the extractant system in which TD d DGA is dissolved, the extraction amount into the organic phase becomes an ideal extraction capacity value as the Nd (III) concentration in the initial aqueous phase increases without generating a third phase. It shows that we are approaching.
図１よりＤＧＡ化合物による硝酸溶液からのＡｍ（III）の抽出分配比はかなり高く、また図２ではＴＤｄＤＧＡのような長いアルキル鎖を持つＤＧＡ化合物の場合、第三相を生成することがなく、有機相への金属抽出量が大きくなることなどが分かった。 From FIG. 1, the extraction partition ratio of Am (III) from the nitric acid solution by the DGA compound is quite high, and in FIG. 2, in the case of a DGA compound having a long alkyl chain such as TD d DGA, a third phase can be formed. It was found that the amount of metal extracted into the organic phase increased.
なお、ＤＧＡ化合物はこれまでに、４価のアクチノイドイオンは３価イオンよりも高い選択性を示していることが確認されており、４価イオンについても３価イオンと同等以上の性質をもつとみなされる。 DGA compounds have been confirmed so far that tetravalent actinoid ions have higher selectivity than trivalent ions, and tetravalent ions have properties equal to or higher than trivalent ions. It is regarded.
ＳＦ溶解液又はＨＬＬＷより効率的に高濃度の３、４価アクチノイドイオンを溶媒抽出法により、第三相の生成無しに抽出剤の最大限分離除去できる。その結果、プロセス評価が容易になり、効率的な抽出剤の取り扱いができ、コスト削減に繋がる。 The extractant can be separated and removed to the maximum extent without the formation of the third phase by the solvent extraction method with a higher concentration of tri- and tetravalent actinoid ions than SF solution or HLLW. As a result, process evaluation is facilitated, the extractant can be handled efficiently, and costs are reduced.
Claims (2)
高い親油性を示すＮ，Ｎ，Ｎ’，Ｎ’−テトラドデシル１，３−オキサペンタンジアミド（ＴＤｄＤＧＡ）をドデカンに希釈した抽出用溶媒を用いることにより、第三相の生成を抑制することを特徴とする方法。 In a method for solvent extraction of Nd (III) from a nitric acid aqueous solution that is a spent fuel (SF) solution or a high-level radioactive waste liquid (HLLW),
By using an extraction solvent in which N, N, N ′, N′- tetradodecyl 1,3-oxapentanediamide (TDdDGA) showing high lipophilicity is diluted in dodecane, the formation of the third phase is suppressed. Feature method.
A spent fuel (SF) solution or high-level radioactive liquid waste (HLLW) containing N, N, N ′, N′-tetradodecyl 1,3-oxapentanediamide (TDdDGA) and using dodecane as a solvent. Extractant for solvent extraction separation of Nd (III) from nitric acid aqueous solution.
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